Selected n-substituted diazoles and diazines and processes for preparing same



United States Patent US. Cl. 260251 Claims ABSTRACT OF THE DISCLOSURECompounds having the formula Y CH and methods of preparing suchcompounds by reacting a polyamine, formaldehyde and 2-nitropropane. Rand R are hydrogen or lower alkyl, Y is N0 or NH n is 0 or 1', and R isa radical containing from about 1 to carbon atoms selected from thegroup consisting of aryl, alkyl, cycloalkyl and This invention relatesto novel compounds and to their production. The novel compounds of thepresent invention are of the structural formula where R is hydrogen oralkyl, e.g. lower alkyl; R is hydrogen or alkyl, e.g. lower alkyl; n is0 or 1; Y is N0 or NH and R is a substituted or unsubstitutedhydrocarbon radical generally containing from about 1 to 25 carbonatoms, such as aryl, e.g. phenyl, tolyl, Xylyl and naphthyl, alkyl, e.g.dodecyl and lower alkyl, e.g. methyl, ethyl, butyl and amyl, cyloalkyl,e.g. cyclohexyl and cycyopentyl and the radical where Y is N0 or NH Inaddition to use as intermediaries in the production of amino compounds,the novel nitro compounds of the present invention exhibit antibacterialand antifungal activity. The amino compounds may be used as oiladditives or as corrosion inhibitors.

The process of the present invention for the production of such nitroand amino compounds can be illustrated by reference to the preparationof 1,3-bis(2-nitroisobutyl)imidazolidine and 1,3-bis(2-aminoisobutyl)imidazolidine. One mole of ethylenediamine is reacted with about threemoles of formaldehyde and about two moles of 2-nitropropane. Thereaction which occurs can be represented by the following equation.

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Equation I N02 CHr-CH BHCH 2CH3CH-CH3 NHz NHz CI'I2 CH2 l l CH3 Afterthe reaction, the 1,3-bis(2-nitroisobutyl)imidazolidine can be isolatedfrom the, reaction mixture if it is the desired product. If, however,l,3-bis(2-aminoisobutyl)imidazolidine is the desired product, thel,3-bis(2- nitroisobutyl)imidazolidine, either in the reaction mixtureor in separated form, is reduced with hydrogen and1,3-bis(2-aminoisobutyl)imidazolidine is isolated from the resultingreaction mixture. The reduction process is represented by the followingequation.

In place of ethylenediamine, other amines, including substituteddiamines and polyamines, can be used to give analogous compounds. Suchamines and polyamines may be represented by the general structuralformula where R, R, and n have the same meaning given above and R ishydrogen or a substituted or unsubstituted hydrocarbon radicalcorresponding to R described above as generally containing from about 1to 25 carbon atoms, such as aryl, e.g., phenyl, tolyl, xylyl andnaphthyl, alkyl, e.g., dodecyl and lower alkyl, e.g., methyl, ethyl,butyl and amyl, cycloalkyl, e.g., cyclohexyl and cyclopentyl. Examplesof such amino and substituted amino compounds include ethylenediamine,1,2 propanediamine, 1,3-propanediamine, 1,2-butanediamine, N-is0pr0py1-2- methyl-1,2-propanediamine, N -cyclohexyl-2-methyl-1,2-propanediamine, N -phenylethylenediamine, etc.

As illustrated by the general formula used above to designate the amineused in the reaction of the present invention, the present invention isnot limited to the production of 1,3-bis(nitroalkyl)-imidazolidines,i.e. compounds from amines having two primary amino groups. Amineshaving one primary amino group and a secondary amino group, i.e. NHRcyclize with the addition of the nitro compound at the primary aminogroup.

The molar proportions of the reactants used vary according to the aminestarting material. When an amine having two primary amino groups is usedas the starting material, about two moles of the nitroalkane and aboutthree moles of formaldehyde are used in the reaction for each mole ofamine to be reacted. If the amine contains a secondary amino group,generally about 1 mole of the nitro compound and two moles offormaldehyde are used per mole of amine.

The reaction of the present invention can be considered substantiallycomplete when about three moles, or two, respectively, of the aldehydehave been consumed for each mole or amine. The time necessary forcompletion of the reaction depends principally upon the startingmaterials, temperature, etc. and is usually from about 0.5 to about 8hours. Generally from about 2 to 4 hours is sufficient.

The reaction of the present invention is conveniently carried out at atemperature somewhat above the melting point of the desired product,usually from room temperature to about 150 C., and preferably from about50 to 120 C. After completion of the reaction, the reaction mixture maybe cooled and the nitro compound separated from the reaction mixture byfiltration, for example. The compounds may be separated from thereduction mixture produced according to Equation II by distillation orcareful rectification of the reduction mixture. The reduction can beaccomplished by contacting the nitro compound with sufficient hydrogenin the presence of a reducing catalyst e.g. Raney nickel, underhydrogenation conditions generally including temperatures from about 30to 120 C. and pressures from about atmospheric to 1500 p.s.i.

EXAMPLES I-V The following procedure shown with reference to theproduction of 1,3-bis(2-nitroisobutyl)imidazolidine and1,3-bis(2-aminoisobutyl)imidazolidine is followed for each of Examples Ithrough V and summarized in Tables I and II.

Production of 1,3 -bis (2-nitroisobutyl imidazolidine To 222 ml. of 37%aqueous formaldehyde solution and 180 g. of 2-nitropropane in a stirred3-necked flask, 77 gms. of a 78% solution of ethylenediamine was addedslowly at 55 to 60 C. The reaction mixture was stirred with slightheating to hold the temperature at 55 to 60 C. for 3 hours, then it wascooled for 2 hours in the refrigerator. The cooled mixture was filteredand 261 gms. of white l,3-bis(2-nitroisobutyl)imidazolidine crystalsmelting at 49 to 55 C. were recovered. These could be convenientlyrecrystallized from isopropyl alcohol.

In cases where the nitroamine was not a solid the organic layer of thereaction mixture was concentrated at reduced pressure, but not furtherpurified.

Production of 1,3-bis(Z-aminoisobutyl)imidazolidine One hundred andthirty-seven grams of 1,3-bis'(2-nitroisobutyl)irnidazolidine in 600 ml.of methanol was reduced at 40 C. and 1000 p.s.i. of hydrogen in thepresence of 25 gms. of Raney nickel for about 4 hours. The reductionmixture was filtered and concentrated at reduced pressure to give 101gms. of product. This was then distilled at as high a vacuum as could beobtained (about 200 to 400 microns) to give a 69 gm. cut of 1,3-bis(2-aminoisobutyl) imidazolidine boiling at 115 to 118 C.

Average wt. loss Inhibitor content (p.p.m.):

(percent) 0 0.05 1 500 0.043 1000 0.042 15 00 0.025

These figures show that 1500 p.p.m. of N N -bis(2-aminoisobutyl)imidazolidine reduced the corrosion rate by aboutone-half under the conditions of the experiment.

It is claimed:

1. Compounds having the formula where R is selected from the groupconsisting of hydrogen and lower alkyl, R' is selected from the groupconsisting of hydrogen and lower alkyl, Y is selected from the groupconsisting of N0 and NH n is an integer selected from the groupconsisting of 0 and l, and R is a radical selected from the groupconsisting of cyclohexyl and alkyl hydrocarbon radicals of about 1 to 25carbon atoms and radicals of the formula where Y has the same meaninggiven above.

2. The compounds of claim 1 wherein Y is N0 3. The compounds of claim 1wherein Y is NH 4. The compound having the formula TABLE I.NITROAMINESFROM AMINES, 2-NITROPROPANE (2-NP) AND FORMALDEHYDE (CHzO) Moles PercentN Percent 0 Percent H Yield, M.P., Example Amine 2-NP CHzO percent 0.Theory Found Theory Found Theory Found Ethylenediamine 2 3 61-63 20. 4320. 35 48. 16 48. 28 8. 09 7. 9 8 II. 1,2-propanediamine. 2 3 93 19. 4319. 85 III 1,3-propanediamine- 2 3 83 6 19. 43 19. 35 49. 98 50. 11 8.39 8. 58 IV- N -isopropyl-2 methyl-1,2-propanediamine 1 2 98 17. 34 17.19 59. 23 58. 83 10. 3G 9. 83 V N-cyelohexyl-2-methyl-1,2-propanediamine 1 2 97 14. 83 14. 97

TABLE II.AMINES FROM CORRESPONDING NITROAMINES OF TABLE I Percent N Neut. Eq. Yield, B.P., 0. percent at microns Theory Found Theory FoundNitroamine example The following illustrate the advantageous corrosionin- 70 6, The compound having the formula hibiting characteristics forinstance on a metal, e.g. steel, surface provided by the novel compoundsof the present CH3 (3H2 (3114113 CH3 invention. I

CH3-CCH2N NCHzC--OH Corrosion tests were carried out on pollshed /2 x 4"75 N O 2 C 2 N 0 2 carbon steel (No. 1010) strips immersed in 5% brine7. The compound having the formula CH2 (3H (1)111 (1311 (I111,CH3(|1CH2N N-CH2-(|1C1I3 N02 CH2 N02 8. The compound having the formulaCH2 (I311; (IJIIQ CH2 CH3 CH;-!CCII2-N N-CH2C-Cil NH2 CH3 NH2 9. Thecompound having the formula CH CH;/( 3-CH CH OI-I1 \l I I-CH2-C-cm CH3cz l loz 10. The compound having the formula CH CH CH2(|)CH3 CH3 (DH-N r-I0I-I2CcHa JH CH NH;

11. The compound having the formula CH CH CI g CH2 CI-Iz--( 3-CH on;(3H2 (DH-N N-CHT-(ICH CH2 011 N02 12. The compound having the formulaCH2 CH3 Cfiz \CH2 CH2CIICH3 CH (I311: CHN NCH2CCH3 Cz CH2 ILIH2 13. Thecompounds of claim 1 wherein R is lower alkyl.

14. The compounds of claim 1 wherein R is a cyclohexyl radical.

15. The compounds of claim 1 wherein R is ([3113 CH ('JCH 16. A processfor producing the compounds of claim 2 comprising reacting an aminehaving the formula where R, R, and n have the same meaning as in claim 2and R is selected from the group consisting of hydrogen, cyclohexyl andalkyl hydrocarbon radicals of about 1 to 25 carbon atoms with from about2 to 3 moles of formaldehyde and from about 1 to 2 moles of2-nitropropane for each mole of an amine, under reaction conditionsincluding temperatures from about room temperature to 150 C. to producethe compounds of claim 2.

17. A process for producing the compounds of claim 13 wherein Y is N0comprising reacting an amine having the formula where R and R are eachselected from the group consisting of hydrogen and lower alkyl, 11 is aninteger selected from the group consisting of 0 and 1 and R is loweralkyl, with about 2 moles of formaldehyde and about 1 mole of2-nitropropane for each mole of said amine, under reaction conditionsincluding temperatures from about room temperature to C. to produce thecompounds of claim 15 wherein Y is N0 18. A process for producing thecompounds of claim 14 wherein Y is N0 comprising reacting an aminehaving the formula where R and R are each selected from the groupconsisting of hydrogen and lower alkyl, n is an integer selected fromthe group consisting of 0 and 1, and R is cyclohexyl, with about 2 molesof formaldehyde and about 1 mole of Z-nitropropane for each mole of saidamine, under reaction conditions including temperatures from about roomtemperature to 150 C. to produce the compounds of claim 16 wherein Y isN0 19. A process for producing the compounds of claim 15 wherein Y is N0comprising reacting an amine having the formula where R and R are eachselected from the group consisting of hydrogen and lower alkyl and n isan integer selected from the group consisting of 0 and 1 with about 3moles of formaldehyde and about 2 moles of 2-nitropropane for each moleof said amine, under reaction conditions including temperatures fromabout room temperature to 150 C. to produce the compounds of claim 17wherein Y is N0 20. A process for producing a compound of claim 3 whichcomprises reacting an amine having the formula wherein R, R and n havethe same meaning as in claim 3 and R is selected from the groupconsisting of hydrogen, cyclohexyl and alkyl hydrocarbon radicals ofabout 1 to 25 carbon atoms, with about 2 to 3 moles of formaldehyde andabout 1 to 2 moles of 2-nitropropane for each mole of said amine, underreaction conditions including temperatures from about room temperatureto 150 C. to produce a compound having the formula N02 CH R. V. RUSH,Assistant Examiner US. Cl. X.R.

@ 3 3 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3, 671 Dated March 24, L970 Inventor(s) Edward B- HOdge It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

Column 3, Table 1, Line 9: "N isopropyl2 methyl-1, 2-

propanedia mine" should be --N -isopropyl-2- methyl-1,2-propanediamine--.

Column 6, line 3: "15" should be -l3-.

Column 6, 1inel8: "16" should be "14.

Column 6, line 32: "l7" should be --l5-.

AUG 251570 (SEAL) Atteat:

EdwardM. Fletcher, It. I E. I m.

Gonmissioner of Patents

